AMINE AND NON-AMINE DERIVATIZED POLYARYLETHERKETONE RANDOM AND BLOCK COPOLYMERS

Abstract

The present invention provides a method of preparing a polyaryletherketone copolymer (e.g. a random or block copolymer), said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer in a reaction medium comprising: (a) a Lewis acid and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof; and polymers produced therefrom.

Claims

1. A method of preparing a polyaryletherketone copolymer, said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer in a reaction medium comprising: (a) a Lewis acid, and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof; wherein said comonomer is not a compound represented by formula: ##STR00018##

2. A method of preparing a polyaryletherketone block copolymer, said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer in a reaction medium comprising: (a) a Lewis acid, and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof; wherein said monomer system suitable for forming the aryletherketone units is polymerised separately to the comonomer.

3. A method of preparing a polyaryletherketone copolymer, said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer comprising an ester, sulphone and/or amide group in a reaction medium comprising: (a) a Lewis acid, and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof.

4. A method of preparing a polyaryletherketone copolymer, said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer in a reaction medium comprising: (a) a Lewis acid, and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof; wherein said aryletherketone unit does not comprise -Ph-O-Ph-C(O)-Ph-O-Ph-C(O)-Ph-C(O).

5. A method of preparing an amine-functionalised polyaryletherketone copolymer, said method comprising: polymerising (i) a monomer system suitable for forming aryletherketone units and (ii) a comonomer in a reaction medium comprising: (a) a Lewis acid, and (b) a controlling agent comprising an aromatic carboxylic acid, an aromatic sulphonic acid, or a derivative thereof; and adding a capping agent comprising NR.sub.2, NRH or a protected amine group to said reaction medium.

6. The method of claim 5, wherein said comonomer comprises an ester, imide, sulphone and/or amide group.

7. The method of claim 5, wherein the polyaryletherketone copolymer is a block copolymer, and said monomer system suitable for forming the aryletherketone units is polymerised separately to the comonomer.

8. The method of claim 5, wherein said comonomer comprises an ester, sulphone and/or amide group.

9. The method of claim 5, wherein said aryletherketone unit does not comprise -Ph-O-Ph-C(O)-Ph-O-Ph-C(O)-Ph-C(O).

10. The method of claim 1, wherein said reaction medium further comprises a capping agent comprising NR.sub.2, NRH or a protected amine group.

11. The method of claim 5, wherein said monomer system suitable for forming the aryletherketone units is polymerised separately to, or simultaneously with, the comonomer.

12. The method of claim 5, wherein said aryletherketone units are independently selected from the group consisting of: ArOArC(O), ArOArC(O)ArC(O), ArOArOArC(O), ArOArOArC(O)ArC(O), and ArOArC(O)ArOArC(O)ArC(O), wherein each Ar is independently an aromatic moiety.

13. The method of claim 12, wherein each Ar is independently selected from the group consisting of substituted or unsubstituted mononuclear aromatic moieties and substituted or unsubstituted polynuclear aromatic moieties.

14. The method of claim 5, wherein said controlling agent is one or more of: (i) Ar(COOX).sub.y; (ii) Ar(SO.sub.3X).sub.y; (iii) (ArCOO.sup.).sub.zM.sup.z+; or (iv) (ArSO.sub.3.sup.).sub.zM.sup.z+ wherein Ar is an aromatic group compatible with components remained in the reaction medium; each X independently is a hydrogen atom or an organic group (R); each y independently is 1, 2 or 3; each M independently is a metal; and each z independently is an integer equal to charge on the metal ion (M.sup.z+).

15. The method of claim 5, wherein said capping agent is represented by formula (Z).sub.aAr(X).sub.b wherein: each X is independently selected from the group consisting of OAr, C(O)Cl, C(O)ArOAr and OAr[C(O)ArOAr].sub.cH wherein each Ar is independently an aromatic moiety; c is an integer, Z is a protected amine group; a is 1 to 5, and b is 1 to 5.

16. The method of claim 5, wherein said reaction medium comprises two or more types of comonomers.

17. A polyaryletherketone copolymer obtained by the method according to claim 5.

18. Particles of the polyaryletherketone copolymer obtained by the method according to claim 5.

19. The polyaryletherketone copolymer of claim 17, wherein the polyaryletherketone copolymer is a polyaryletherketone block copolymer.

20. The method of claim 5, wherein the polyaryletherketone copolymer is an amine functionalised polyaryletherketone copolymer, and said amine-functionalised polyaryletherketone copolymer is neither an amine-functionalised polyaryletherketone-imide copolymer nor an amine-functionalised polyaryletherketone-sulphone copolymer.

21. The polyaryletherketone copolymer of claim 17, wherein said polyaryletherketone copolymer is an amine-functionalised polyaryletherketone copolymer.

22. The polyaryletherketone copolymer of claim 19, wherein said polyaryletherketone copolymer is in a particulate form.

23. The particles of claim 18, wherein said polyaryletherketone copolymer is a block polyaryletherketone copolymer.

24. The method of claim 15, wherein each Z is independently selected from the group consisting of NHL, NRL and NL.sub.2, and each L is a leaving group independently selected from the group consisting of acetyl, haloacetyl, carbonate, sulphonyl, halosulphonyl, SO.sub.2R, c is 1 to 10, each R is independently an aliphatic or aromatic group, a is 1, 2 or 3, and b is 1, 2 or 3.

Description

EXAMPLE 1

Amine-Terminated Random Imide-Sulphone-Ketone Copolymer (Dispersion)

[0194] To a 2000 ml reaction flask equipped with a mechanical stirrer, having been purged with dry nitrogen, was added 800 ml of dry dichloromethane. Having cooled the dichloromethane to 20 C. 476 g (3.57 mols) of anhydrous aluminium chloride was added. Also at 20 C. was added 175.75 g (1.44 mols) of benzoic acid taking care not to let the temperature of the slurry to rise above 10 C. This was followed by 100.31 g (0.1556 mol) of pure bis-imide monomer (EIEIE)

##STR00014##

along with 200 ml of dichloromethane to wash in any powder residues; the temperature was maintained below 10 C. This was followed by 69.69 g (0.1902 mol) of 4,4-diphenoxydiphenylsulphone (ESE) also at 10 C. and also washed into the reactor with 200 ml of dichloromethane. This was followed by 73.13 g (0.3602 mols) of terephthaloyl chloride (KK) was added to the slurry along with a further 100 ml of dichloromethane to was in any powder residues. Finally the protected amine end-capper CF.sub.3CONH-Ph-O-Ph (CF.sub.3-EC) 8.0928 g (0.0288 mol) was added and washed into the reactor with 25 ml of dichloromethane.

[0195] Whilst stirring at 450 rpm the reaction mass was warmed to 0 C. and maintained for 30 mins. The mass was then warmed to +20 C. and maintained for 6 hours. During this period, the colour of the reaction mass was dark orange. During the polymerisation, hydrogen chloride was evolved which was trapped and disposed of safely.

[0196] After stirring at room temperature for 6 hours the reaction mass was poured into 5 litres of iced water (care must be taken to avoid the temperature of the decomplexing mixture rising above room temperature). The aqueous mass was then stirred at room temperature for 4 hours or until all of the orange colouration had disappeared leaving a pale cream mass.

[0197] Having transferred the mass to a suitable vessel, the vessel was heated and the dichloromethane distilled off. The yield of the recovered dichloromethane was 92% by weight. Having removed all of the dichloromethane, the mass was brought to reflux and refluxed for 1 hour whereupon the suspension was filtered whilst hot. While the filtrate was left to cool the white polymer solid was added to a further 3 litres of deionised water containing 300 ml of concentrated hydrochloric acid and brought to reflux, the reflux maintained for 1 hour. This was repeated a further two times, without the hydrochloric acid, and in each case the filtrate was added to the initial filtrate and allowed to cool. The polymer powder was refluxed in deionised water containing 100 ml of 0.88 ammonia. Finally the polymer powder was refluxed in deionised water with no additives. The polymer powder was then dried overnight at 80 C. in air and then at 200 C. overnight under vacuum. On cooling, benzoic acid crystallised from the combined filtrates. The yield of benzoic acid was enhanced by chilling the filtrates to 5 C. The yield of the recovered benzoic acid was 77% by weight.

[0198] The Inherent Viscosity (IV) of the polymer was determined by dissolving approximately 25 mg of the polymer in 25 ml of concentrated sulphuric acid at 25 C. The IV of this sample was 0.92 dig. The structure of the polymer was confirmed by .sup.13C NMR. The presence of amine terminations was confirmed using infra-red spectroscopy.

[0199] The T.sub.g of the polymer was 198 C., no T.sub.m was observed.

EXAMPLE 2

Amine-Terminated Random Imide-Sulphone-Ketone Copolymer (Gel)

[0200] Example 1 was repeated substituting the benzoic acid for dimethyl sulphone where the quantity of dimethyl sulphone was 50.85 g (0.5404 mol) and the amount of aluminium chloride was 344 g (2.58 mol). The polymer was isolated as a gel and decomplexed using a Waring blender. None of the dimethyl sulphone was recovered and only 20% of the dichloromethane.

[0201] The IV of the polymer was 0.97 dl/g and the T.sub.g 197 C. The polymer was characterised as in example 1.

EXAMPLE 3

Amine-Terminated Random PEKEKK-PESEKK Copolymer (Gel)

[0202] The method of example 1 was repeated using the following reagents:

4,4-diphenoxybenzophenone (EKE): 96.05 g (0.2621 mol)
4,4-diphenoxydiphenylsulphone (ESE): 128.81 g (0.3204 mol)
1:1 mixture of terephthaloyl and isophthaloyl chlorides: 120.67 g (0.5944 mol)
Dimethyl sulphone: 82.2 g (0.8734 mol)
Aluminium chloride: 423.14 g (3.17 mol)
CF.sub.3CONH-Ph-O-Ph (CF.sub.3-EC): 6.6878 g (0.0238 mol)

[0203] The IV of the polymer was 1.47 dL/g. The T.sub.g of the polymer was 173 C.

EXAMPLE 4

Amine-Terminated Random PEKEKK-PEIEIEKK Copolymer (Gel)

[0204] The method of example 1 was repeated using the following reagents:

4,4diphenoxybenzophenone (EKE): 94.54 g (0.258 mol)
Bis imide monomer EIEIE: 83.16 g (0.129 mol)
Terephthaloyl chloride: 85.25 g (0.4199 mol)
Dimethyl Sulphone: 79.06 g (0.84 mol)
Aluminium chloride: 394 g (2.95 mol)
CF3-CONH-Ph-O-Ph (CF.sub.3-EC): 18.4898 g (0.0658 mol)

[0205] The IV of the polymer was 0.62 dL/g. The T.sub.g was 180 C. and the T.sub.m 344 C.

EXAMPLE 5

Amine-Terminated Random PEKK-PEIEIEKK Copolymer (Gel)

[0206] Example 4 was repeated replacing the 4,4-diphenoxybenzophenone with 1,4-bis(4-phenoxybenzoyl)benzene (EKKE): 121.39 g (0.258 mol)

[0207] The amount of aluminium chloride used was 434 g (3.25 mol)

[0208] The IV of the polymer was 0.64 dL/g. The T.sub.g was 182 C. and the T.sub.m 346 C.

EXAMPLE 6

Amine-Terminated Random PEKEKK-PEAm-1,3-AmEKK Copolymer (Gel)

[0209] ##STR00015##

[0210] The method used is example 1 was repeated using the following reagents. 4,4-diphenoxybenzophenone (EKE): 54.58 g (0.1489 mol)

EAm-1,3-AmE: 70.96 g (0.1489 mol)
Terephthaloyl chloride: 63.00 g (0.3103 mol)
Dimethyl sulphone: 58.35 g (0.62 mol)
Aluminium chloride: 268.99 g (2.02 mol)
CF.sub.3CONH-Ph-O-Ph (CF.sub.3-EC): 7.025 g (0.025 mol)

[0211] The IV of the resultant polymer was 0.97 dL/g

[0212] The T.sub.g of the polymer was 200 C., the T.sub.m was 342 C.

EXAMPLE 7

Block PEKEKK-PESEKK Copolymer (Dispersion)

[0213] Using a 1000 ml reactor set up as in example 1 the following reagents were used.

4,4diphenoxybenzophenone (EKE): 25 g (0.0682 mols)
4,4-diphenoxydiphenylsulphone (ESE): 27.46 g (0.0682 mols)
Terephthaloyl chloride: 26.86 g (0.1323 mols)
Benzoic acid: 64.63 g (0.5292 mols)
Aluminium chloride: 148.97 g (1.12 mols)
Benzoyl chloride: 1.1526 g (8.210.sup.3 mols)

Dichloromethane: 600 ml

[0214] To the cooled dichloromethane (300 ml) was added all of the aluminium chloride. This was followed by all of the benzoic acid ensuring the temperature of the slurry remained below 10 C. Also at 10 C. was added all of the 4,4diphenoxybenzophenone and powder residues were washed into the reaction vessel with 50 ml of dichloromethane. To the yellow suspension was then added 10.389 g (0.0512 mols) of the terephthaloyl chloride. This should give a PEKEKK repeat unit of 4. While stirring at 450 rpm the reaction mass was warmed to +10 C. and maintained for 1.5 hours. After this time all of the 4,4-diphenoxydiphenylsulphone and the remaining terephthaloyl chloride was added and any powder residues washed into the reaction vessel with the remaining dichloromethane. The reaction mass was then heated to +20 C. and maintained for 4 hours. The work-up used was as in example 1. The IV of the polymer was 0.91 dL/g. The T.sub.g of the polymer was 185 C. and the T.sub.m 362 C. By comparison the T.sub.g of the same fully random copolymer was 176 C. and the polymer was essentially amorphous.

EXAMPLE 8

Amine-Terminated Block PEKEKK-PESEKK Copolymer (Dispersion)

[0215] Example 7 was repeated using the following reagents. This gives an NH.sub.2 terminated polymer.

4,4diphenoxybenzophenone (EKE): 25 g (0.0682 mols)
4,4-diphenoxydiphenylsulphone (ESE): 27.46 g (0.0682 mols)
Terephthaloyl chloride: 28.54 g (0.1406 mols)
Benzoic acid: 68.68 g (0.5624 mols)
Aluminium chloride: 148.97 g (1.12 mols)
CF.sub.3CONH-Ph-O-Ph (CF.sub.3-EC): 2.3604 g (8.410.sup.3 mols)

Dichloromethane: 600 ml

EXAMPLE 9

Block PEKEKK-PEIEIEKK Copolymer (Dispersion)

[0216] ##STR00016##

[0217] Using a 1000 ml reactor set up as in example 1 the flowing reagents were used.

4,4-diphenoxybenzophenone (EKE): 20 g (0.0546 mols)
Bis-imide EIEIE: 35.186 g (0.0546 mols)
Terephthaloyl chloride: 21.06 g (0.1037 mols)
Benzoic acid: 50.66 g (0.4148 mols)
Aluminium chloride: 143.24 g (1.07 mols)
Benzoyl chloride: 1.5463 g (0.011 mols)

Dichloromethane: 600 ml

[0218] As in example 7 where in the first phase all of the 4,4diphenoxybenzophenone was reacted with 8.3137 g (0.04095 mols) of terephthaloyl chloride giving a PEKEKK block of 4 repeat units.

[0219] The IV of the resultant polymer was 0.84 dL/g. The T.sub.g of the polymer was 186 C. the T.sub.m was 360 C. By contrast the random copolymer is essentially amorphous.

EXAMPLE 10

Amine-Terminated Block PEKEKK-PEIEIEKK Copolymer (Dispersion)

[0220] ##STR00017##

[0221] As in example 9 using the following reagents:

4,4-diphenoxybenzophenone (EKE): 20 g (0.0546 mols)
Bis-imide EIEIE: 35.186 g (0.0546 mols)
Terephthaloyl chloride: 23.35 g (0.1150 mols)
Benzoic acid: 56.18 g (0.46 mols)
Aluminium chloride: 154.09 g (1.156 mols)
CF3-CONH-Ph-O-Ph (CF.sub.3-EC): 3.259 g (0.0116 mols)

Dichloromethane: 600 ml